Biocidal compositions comprising mixtures of haloproynyl compounds and sulfur containing triazines

ABSTRACT

This invention is directed to a broad spectrum fungicide/algaecide composition which comprises a mixture of (a) at least one halopropynyl compound and (b) at least one sulfur-containing s-triazine, said mixture provided in an amount to prevent and/or protect a substrate from attack by one or more fungal and/or algael organisms. The composition can be used broadly in industrial systems and more particularly with substrates such as paints, coatings, stucco, concrete, stone, cementaceous surfaces, wood, caulking, sealants, textiles, and the like.

This application is a divisional of application Ser. No. 08/436,554,filed May 8, 1995, now U.S. Pat. No. 5,707,929.

FIELD OF THE INVENTION

This invention is directed to a biocidal composition and particularly asynergistic mixture or combination of a halopropynyl compound and asulfur-containing s-triazine.

BACKGROUND OF THE INVENTION

Both exterior and interior surfaces and substrates of all types, whenexposed to common environmental conditions, e.g. moisture, are prone toattack, discoloration and various kinds of destruction by fungal andalgael organisms. As a result, there is a great need and requirement foran effective and economical means to protect for extended periods oftime both exterior and interior surfaces and various type substratesfrom the deterioration and destruction caused by such microorganisms.

Materials which need protection with a suitable antimicrobialcomposition controlling both fungal and algael microorganisms and theiradverse effects include paints, coatings, stucco, concrete, stone,cementaceous surfaces, wood, caulking, sealants, and textiles as well asmaterials and other substances which may be attacked by fungi and/oralgae.

Commercial products designed for the simultaneous control of fungi andalgae on such substrates are available, but such products suffer from anumber of disadvantages and especially their inability to maintainsufficient activity after leaching by water.

In addition, such products currently available in the marketplace aregenerally supplied as normally water-insoluble powders, as pastes, or asflowable dispersions which are difficult to incorporate in a manner toinsure maximum effectiveness. On the other hand, an effectivecomposition in the form of a solution would be highly desirable havingadvantages for ease of handling and incorporation in end use productsand to insure proper distribution of the biocide on or in the surfacesand substrates to be protected, thus maximizing microbiologicalperformance.

Thus, a broad spectrum biocide composition highly effective against bothfungi and algae, and which is essentially unaffected by leaching withwater, in an environmentally, toxicologically suitable liquid media hasmany advantages and is desirable for a wide number of uses in industry.

With respect to compositions and/or mixtures, methods of manufactureand/or uses and applications of combinations of fungicides andalgaecides, the prior art and references describing these combinationsis limited.

There are a number of organic compounds and especially certaincarbamates, such as the halopropynyl carbamates which are knownprimarily for their fungicidal activity. 3-iodo-2 propynyl butylcarbamate, hereinafter referred to as IPBC, is the best known and themost widely used of the known haloalkynyl carbamate fungicides. Inaddition to its fungicidal activity, IPBC also has been associated withalgaecidal activity. In this regard, Great Britain Patent 2,138,292 andU.S. Pat. Nos. 4,915,909 and 5,082,722 contain such disclosures. IPBC isa highly active broad spectrum fungicide. Nevertheless, its spectrum ofaction is sometimes incomplete against the broad range of naturallyoccurring fungal species. For this reason, U.S. Pat. No. 5,389,300describes using a phenol derivative, such as o-phenylphenol, with aniodopropargyl compound, such as IPBC, for protecting freshly sawn timberfrom such pests.

Certain s-triazines are known for their algaecidal activity. They havebeen found to be especially effective for use in agriculturalapplications. One such example of this algacide is N² tertbutyl-N⁴-ethyl-6-methylthio-1,3,5-triazine-2,4 diyldiamine and a second suchexample is 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine.U.S. Pat. No. 4,710,220 for example, describes formulations containing apolyethoxylated compound and certain s-triazines, with N² -tert-butyl-N⁴-ethyl-6-methylthio-1,3,5-triazine-2,4-diyldiamine, hereafter referredto as Terbutryn, as one example. Even so, Terbutryn is probably morewidely known as a herbicide, and in particular, is widely disclosed foruse as a herbicide in combination with a variety of other compounds. Forexample, in U.S. Pat. No. 3,957,481 it is used in combination withmetobromuron for controlling weeds when cultivating leguminosae andsolana; in U.S. Pat. No. 4,640,705 and Great Britain Patent 2,126,092 itis used in combination with trifluralin and ethylfluralin respectively,for preemergent control of weeds, particularly blackgrass, in cerealcrops and in French Patent 2,438,970 it is used with neburon andnitrofen to control weeds in winter wheat. Nowhere, however, has it beensuggested to combine Terbutryn with a halopropynyl compound andparticularly a haloalkynyl carbamate fungicide for any purpose.

In this regard, while U.S. Pat. No. 4,721,523 describes a herbicidalcombination of certain widely-known carbamate derivatives with aphotosynthesis-inhibiting compound, including as one of nine possiblecompound classes certain triazine derivatives (identifying Terbutryn asone of a dozen examples), the disclosed carbamates do not include thehaloalkynyl carbamates.

In a similar fashion, while U.S. Pat. No. 5,374,631 describes using amixture of an iodopropargyl compound, including IPBC, with an s-triazineto control fungal and bacterial growth in metalworking fluids, the onlytriazine identified is hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine.

Thus, the prior art has completely failed to appreciate any benefit fromcombining a halopropynyl compound and particularly a haloalkynylcarbamate with a sulfur-containing s-triazine.

BRIEF DESCRIPTION OF THE INVENTION

The present invention is based on the surprising synergistic effect thata combination of a halopropynyl compound, and particularly ahalopropynyl carbamate fungicide, and a sulfur-containing s-triazinealgaecide has on the increased efficacy of the resulting combinedproduct, especially against fungi.

In accordance with a preferred embodiment of the invention, it has nowbeen discovered that synergistic combinations containing in particularboth the fungicide, 3-iodo-2-propynyl butyl carbamate (IPBC) and theherbicide, N² -tertbutyl-N⁴ -ethyl-6-methylthio-1,3,5-triazine-2,4diyldiamine (Terbutryn) gives a surprising and unexpected biocidaleffect against mold and blue-stain fungi. This increased biocidal effecthas especially been shown to occur when the product is used against thefungi Aureobasidium pullulans and Alternaria alternata. This discoveryis of outstanding commercial importance because the increased effect hasespecially been demonstrated after the test samples have been exposed toleaching with water. Particularly surprising is the good effect againstAlternaria alternata, which often is found to be very difficult tocontrol on exposed surfaces such as paints, coatings, stucco, concretestone, cementaceous surfaces, wood, caulking, sealants, textiles, andthe like.

Relative proportions of the two components in compositions according tothe present invention may be varied widely since the combination alsoprovides excellent algaecidal properties. Depending on the degree ofenvironmental pressure on the exposed area, it can be an advantage toselect and adjust the proportions of the two components relevant to anddepending upon which organism is more problematic to control and forwhich maximum protection is desired.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to a synergistic combination of ahalopropynyl compound, particularly a halopropynyl carbamate such asIPBC, and a sulfur-containing s-triazine, particularly Terbutryn.

A halopropynyl compound for use in the present invention can beidentified by the following structure:

    YC.tbd.C--CH.sub.2 X

wherein Y is a halogen, preferably iodine and X can be (1) oxygen whichis part of an organic functional group; (2) nitrogen which is an organicfunctional group; (3) sulfur which is part of an organic functionalgroup; or (4) carbon which is part of an organic functional group.

The functional group of which oxygen is a part is preferably an ether,ester, or carbamate group. The functional group of which nitrogen is apart is preferably an amine, amide, or carbamate group. The functionalgroup of which sulfur is a part is preferably a thiol, thiane, sulfone,or sulfoxide group. The organic functional group of which carbon is apart is preferably an ester, carbamate or alkyl group.

Examples of compounds which may be used as the halopropynyl compoundfungicide of this invention are especially the fungicidally activeiodopropargyl (iodopropynyl) derivatives. In this regard, please seeU.S. Pat. Nos. 3,923,870, 4,259,350, 4,592,773, 4,616,004, 4,719,227,and 4,945,109, the disclosures of which are herein incorporated byreference. These iodopropynyl derivatives include compounds derived frompropargyl or iodopropargyl alcohols such as the esters, ethers, acetals,carbamates and carbonates and the iodopropargyl derivatives ofpyrimidines, tiazolinones, tetrazoles, triazinones, sulfamides,benzothiazoles, ammonium salts, carboxamides, hydroxamates, and ureas.Preferred among these compounds is the halopropynyl carbamate,3-iodo-2-propynyl butyl carbamate. This compound is included within thebroadly useful class of compounds having the generic formulas: ##STR1##

Wherein R is selected from the group consisting of hydrogen, substitutedand unsubstituted alkyl, aryl, alkylaryl, and aralkyl groups having from1 to 20 carbon atoms or from cycloalkyl and cycloalkenyl groups of 3 to10 carbon atoms, and m and n are independently integers from 1 to 3,i.e., not necessarily the same.

Suitable R substituents include alkyls such as methyl, ethyl, propyl,n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl,octadecyl, cycloalkyls such as cyclohexyl, aryls, alkaryls and aralkylssuch as phenyl, benzyl, tolyl, cumyl, halogenated alkyls and aryls, suchas chlorobutryl and chlorophenyl, and alkoxy aryls such as ethoxyphenyland the like.

Especially preferred are such iodopropargyl carbamates as3-iodo-2-propynyl propyl carbamate, 3-iodo-2-propynyl butyl carbamate,3-iodo-2-propynyl hexyl carbamate, 3-iodo-2-propynyl cyclohexylcarbamate, 3-iodo-2-propynyl phenyl carbamate, and mixtures thereof.

Examples of compounds which may be used as the sulfur-containings-triazine component of this invention include the known, algaecidallyactive s-triazine compounds. Those included, without limitation thereto,are N² -tert-butyl-N⁴ -ethyl-6-methylthio-1,3,5-triazine-2,4-diyldiamineand 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine. Thesecompounds are represented by the generic formula: ##STR2## in which R¹,and R² independently of one another are each a C₂ to C₆ alkyl group or aC₃ to C₆ cycloalkyl.

As C₂ -C₆ -alkyl, R¹ and R² are for example: ethyl, propyl, isopropyl,butyl, secbutyl, pentyl, isopentyl, hexyl, 1,2-dimethylpropyl,1,2-dimethylbutyl or 2,3-dimethylbutyl. Particularly preferred arebranched-chain C₃ -C₆ -alkyl groups, for example isopropyl,1,2-dimethylpropyl or tert-butyl.

As C₃ -C₆ -cycloalkyl, R¹ and R² are for example: cyclopropyl,cyclobutyl, cyclopentyl or cyclohexyl, cyclopropyl being preferred.

Preferred sulfur-containing s-triazines of the formula are those whereinR¹ is a branched-chain C₃ -C₆ -alkyl, for example isopropyl,1,2-dimethylpropyl or tert-butyl; or wherein R¹ is cyclopropyl.

Likewise preferred are compounds of the formula wherein R¹ is ethyl orcyclopropyl, and wherein R² is tert-butyl, 1,2-dimethylpropyl orisopropyl.

Relative proportions of the halopropynyl compound and thesulfur-containing s-triazine in the composition can vary widely and anoptimum proportion likely will be affected by the intended applicationand the particular compounds selected. In any event, it is expected thatcompositions containing a little as 1 part of the halopropynyl compoundto 9 parts of the s-triazine and conversely as little as 1 part of thes-triazine to 9 parts of the halopropynyl compound will be useful.Typically, useful compositions will contain from 2:1 to 1:2 parts of thehalopropynyl compound to the s-triazine and more usually from 2:1 to 1:1relative parts by weight.

In accordance with the invention, the combined fungicidal and algaecidalconstituents can be included in a final formulation for use in such enduse applications as paints, coatings, stucco, concrete, stone,cementaceous surfaces, wood, caulking, sealants, textiles, and the like,in a broad range from about 0.004% to 2.0% active concentration. Suchcompositions can be prepared from highly concentrated compositions ofthe active ingredients by appropriate dilution. The optimum useful rangeis about 0.1% to 0.3% of combined products in the final formulations forsuch end use systems. With the use of such modified formulations in enduse systems, it is possible to protect surfaces as well as othersubstrates for extended periods of time against growth from both algaeand fungi.

Compositions of the present invention will generally be formulated bymixing the two active ingredients in a selected proportion with a liquidvehicle for dissolving or suspending the active components. The vehiclemay contain a diluent, an emulsifier and a wetting-agent. Expected usesof the biocidal compositions include protection of wood, paint,coatings, adhesives, paper, textiles, plastics, cardboard, lubricants,caulkings, and the like. An extensive list of potential industries andapplications for the present invention can be found in U.S. Pat. No.5,209,930 which is herein incorporated by reference. The synergisticcombinations of the halopropynyl compound fungicide, particularly ahalo-propynyl carbamate, and the sulfur-containing s-triazine arepreferably formulated as liquid mixtures, but may be provided aswettable powders, dispersions, or in any other suitable product typewhich is desirable and most useful, provided that the synergisticfungicidal and algaecidal activity are not affected. In this regard, thecomposition of the present invention can be provided as a ready-for-useproduct in the form of aqueous solutions and dispersions, oil solutionsand dispersions, emulsions, aerosol preparations and the like or as aconcentrate.

Useful solvents for the halopropynyl compound, particularly thepreferred iodopropynyl butyl carbamate, and sulfur-containings-triazine, especially Terbutryn, combination are several glycol ethersand esters like propylene glycol n-butyl ether, propylene glycoltert-butyl ether, 2(2-methoxymethylethoxy)-tripropyleneglycol methylether, propylene glycol methyl ether, dipropyleneglycol methyl ether,tripropylenelene glycol methyl ether, propylene glycol n-butyl ether andthe esters of the previously mentioned compounds. Other useful solventsare n-methyl pyrrolidone, n-pentyl propionate and dibasic esters ofseveral dicarboxylic acids and mixes thereof.

The preferred solvents for these products are propylene glycol n-butylether, 1-methoxy-2-propanol, and the dibasic isobutyl ester blend ofsuccinic, glutaric and adipic acids.

When preparing formulations of the present invention for specificapplications, the composition also will likely be provided with otheradjuvants conventionally employed in compositions intended for suchapplications such as organic binding agents, additional fungicides,auxiliary solvents, processing additives, fixatives, plasticizers,UV-stabilizers or stability enhancers, water soluble or water insolubledyes, color pigments, siccatives, corrosion inhibitors, antisettlementagents, anti-skinning agents and the like. Additional fungicides used inthe composition are preferably soluble in the liquid vehicle.

According to the present invention, substrates are protected frominfestation by fungal and algael organisms simply by treating saidsubstrate with a composition of the present invention. Such treating mayinvolve mixing the composition with the substrate, coating or otherwisecontacting the substrate with the composition and the like.

A surprising aspect of the invention was found to be that the mixturesof a halopropynyl compound, and particularly a iodopropynyl carbamateand a sulfur-containing s-triazine are especially efficacious incontrolling the mold and blue stain fungi Aureobasidium pullulans andAlternaria alternata. These two organisms are both generally present inair, soil and water, and appear on most surfaces when moisture ispresent. Accordingly, these two fungi are a major commercial problem onsurfaces coated with paints and other wood protection products and onother treated surfaces since in a short time, they can create a veryheavy, dark staining which not only discolors the surface but attacksthe coating and destroys it as well. Thus, such pests have a verydestructive overall effect and a method for their control has long beensought.

The fungi used in the tests, presented hereinafter, were selectedbecause they are among the most problematic staining organisms whichoccur on exposed surfaces. While synergistic effects have beendemonstrated against the specific organisms shown below in Tables 1 and2, many other fungi can be controlled by these novel biocidalcompositions.

The novel compositions of the invention contain, at least, one herbicidefrom the sulfur-containing s-triazine group which is not presently knownto have any fungicidal effect. However, they are highly efficaciousagainst algae growing on the same areas as the mold fungi. Thehalopropynyl compound, and particularly the iodopropynyl carbamate is afungicide used for protection against staining organisms and wooddestroying fungi. With the combination of these two biocides: aherbicide and fungicide it would be expected to obtain a product activeagainst algae and fungi simultaneously. Surprisingly, it was found thatthe activity against the fungi Aureobasidium pullulans and Alternariaalternata was stronger than would be expected from any known data. Thedata obtained from a solution in which the two compounds have beencombined clearly shows that a synergistic and unexpected effect betweenthe two compounds occurs.

The following examples are presented to illustrate and explain theinvention. Unless otherwise indicated, all references to parts andpercentages are based on weight.

EXAMPLES Example 1

The compositions of the invention were found to be effective againstboth algae and fungi. Specifically, algae and fungi which may beinhibited include without limitation, Stichococcus basillaris, Chlorellavulgaris, Chlorella vulgaris var. viridis, Trentepohlia aurea,Aspergillus niger, Aureobasidium pullulans, Alternaria alternata. Thepreferred combination of compounds, including an iodopropynyl carbamateand a sulfur-containing s-triazine were tested in various ratios from2:1 to 1:6.

The biological tests were carried out separately for algae and forfungi. Detailed descriptions of the tests are outlined below.

In the algae test, an algae inoculum was prepared by washing a one-weekold plate of each species into 100 ml isotonic water. The activeformulations were applied on filter paper at the rate of 225 g/m². Aftera drying time of one week, the filter paper was divided into two parts,one part was immersed into tap water at room temperature, leached for 24hours and then dried. The other part was allowed to remain unleached.1.26 cm² discs were cut from the leached and unleached filter paper andplaced on the agar plates. A suspension of 0.5 ml algae was spread overthe plate and the test paper with an appropriate spatula.

The plates were incubated at 15° C. and evaluated after 2 weeks.

When the combination samples were tested against fungi, each sample wascoated upon filter paper in duplicate, and then air dried for 1 week.One of the filter papers was exposed (leached) for 24 hours in roomtemperature tap water and air dried for 24 hours. Each sample was thencut into 1 inch squares of which 2 were placed in petri dishescontaining solidified Malt Agar and seeded with Aspergillus niger,conidia and hypha fragments; 2 were placed in petri dishes containingsolidified Malt Agar and seeded with Aureobasidium pullulans, conidiaand hypha fragments, and 2 were placed in petri dishes containingsolidified Malt Agar and seeded with Alternaria alternata, conidia andhypha fragments. The petri dishes were incubated for a period of 3 weeksat 28 degrees C.

Tables 1 and 2 show the results of the comparative tests which werecarried out as described above. The formulations tested were comprisedof 0.1% of 3-iodo-2-propynyl-butylcarbamate (IPBC), 0.1% and 0.2% of N²tertbutyl-N⁴ -ethyl-6-methylthio-1,3,5-triazine-2,4 diyldiamine(Terbutryn) and mixtures of 0.1% IPBC and 0.1% Terbutryn. Test resultsactually show that unexpected synergistic results in inhibition andgrowth reduction were obtained with the tested mixtures as compared witheffects to be expected or predicted from the individual ingredients whentested against fungi, i.e., Aspergillus niger, Aureobasidium pullulansand Alternaria alternata.

                                      TABLE 1                                     __________________________________________________________________________    COMPARATIVE TEST RESULTS AGAINST ALGAE AND FUNGI                              OF IPBC, TERBUTRYN, AND THE COMBINATION OF                                    IPBC AND TERBUTRYN                                                                      ALGAE*   A. NIGER A. PULLULANS                                                                           A. ALTERNATA                                     % Unleached                                                                          Leached                                                                           Unleached                                                                          Leached                                                                           Unleached                                                                          Leached                                                                           Unleached                                                                          Leached                             __________________________________________________________________________    IPBC    0.1                                                                             4    4   Z10  Z8  Z5   0   Z2   0                                   TERBUTRYN                                                                             0.2                                                                             Z25  Z23 5    5   5    5   5    5                                   IPBC +  0.2                                                                             Z25  Z23 Z12  Z8  Z7   Z4  Z4   Z2                                  TERBUTRYN                                                                     RATIO 1:1                                                                     __________________________________________________________________________     Legend:                                                                       Z = Zone of Inhibition (in mm)                                                0 = No growth                                                                 1 = Trace Growth                                                              2 = Light Growth                                                              3 = Moderate Growth                                                           4 = Heavy Growth                                                              5 = Very Heavy Growth                                                         *Test Algae Mixture: Stichococcus basillaris, Chlorella Vulgaris,             Chlorella Vulgaris var. viridis and Trentepohlia aurea                   

                                      TABLE 2                                     __________________________________________________________________________    COMPARATIVE TEST RESULTS AGAINST ALGAE AND FUNGI                              OF IPBC, TERBUTRYN, AND THE COMBINATION OF                                    IPBC AND TERBUTRYN                                                                      ALGAE*   A. NIGER A. PULLULANS                                                                           A. ALTERNATA                                     % Unleached                                                                          Leached                                                                           Unleached                                                                          Leached                                                                           Unleached                                                                          Leached                                                                           Unleached                                                                          Leached                             __________________________________________________________________________    IPBC    0.1                                                                             4    4   Z10  Z8  Z5   0   Z2   0                                   TERBUTRYN                                                                             0.1                                                                             Z25  Z20 1    5   5    1   5    5                                   IPBC +  0.2                                                                             Z25  Z23 Z12  Z8  Z7   Z4  Z4   Z2                                  TERBUTRYN                                                                     RATIO 1:1                                                                     __________________________________________________________________________     Legend:                                                                       Z = Zone of Inhibition (in mm)                                                0 = No growth                                                                 1 = Trace Growth                                                              2 = Light Growth                                                              3 = Moderate Growth                                                           4 = Heavy Growth                                                              5 = Very Heavy Growth                                                         *Test Algae Mixture: Stichococcus basillaris, Chlorella Vulgaris,             Chlorella Vulgaris var. viridis and Trentepohlia aurea                   

Example 2 LIQUID FORMULATIONS--SYNERGISTIC COMBINATIONS

                  TABLE 3                                                         ______________________________________                                        Ingredient                   % W/W                                            ______________________________________                                        A. 1:1 combination                                                            3-iodo-2-propynyl butyl carbamate                                                                          20                                               N.sup.2 -terbutyl-N.sup.4 -ethyl-6-methylthio-1,3,5-triazine-2,4-diyldiami    ne                           20                                               DBE dibasic ester            3                                                propylene glycol n-butyl ether                                                                             57                                               B. 1:1 combination                                                            3-iodo-2-propynyl butyl carbamate                                                                          20                                               N.sup.2 -terbutyl-N.sup.4 -ethyl-6-methylthio-1,3,5-triazine-2,4-diyldiami    ne                           20                                               Propylene glycol n-butyl ether                                                                             60                                               C. 2:1 combination                                                            3-iodo-2-propynyl butyl carbamate                                                                          26.6                                             N.sup.2 -terbutyl-N.sup.4 -ethyl-6-methylthio-1,3,5-triazine-2,4-diyldiami    ne                           13.4                                             Propylene glycol n-butyl ether                                                                             60                                               D. 1:2 combination                                                            3-iodo-2-propynyl butyl carbamate                                                                          13.4                                             N.sup.2 -terbutyl-N.sup.4 -ethyl-6-methylthio-1,3,5-triazine-2,4-diyldiami    ne                           26.6                                             Propylene glycol n-butyl ether                                                                             60                                               ______________________________________                                    

A suitable reaction vessel equipped with an appropriate mixing unit ischarged with the indicated amounts of solvents in Examples 2A through 2Dof Table 3. The mixing unit is started and the indicated amounts of thecarbamate and triazine compounds were added. Mixing was continued untilthe biocides were completely dissolved. The mixture was then filtered(with filter-aid) before transfer to appropriate containers.

A number of liquid formulations were prepared as described above andwere then incorporated into paints by mixing. The precise composition ofbiocides are set forth in detail in Table 3. They were tested accordingto the method as described in Example 1. The test results showedsynergistic activity against algae and fungi when the combinations oftwo ingredients of carbamate and triazine were used at 0.1 total activelevel. Shown in Table 3 are examples of the preferred solvents used inthe preparation of liquid formulations.

                  TABLE 4                                                         ______________________________________                                        WETTABLE POWDER                                                                                      Parts/Wt.                                              ______________________________________                                        Example 3A - Ingredient                                                       3-iodo-2-propynyl butyl carbamate (IPBC)                                                               520                                                  Silicon dioxide (silica) 50                                                   Aluminum-Silicate (Clay) 363                                                  Sulphonated Napthalene Condensate (Dispersant)                                                         60                                                   Alkylated Napthalene Sulphonate (Dispersant)                                                           7                                                    TOTAL                    1000                                                 Example 3B - Ingredients                                                      N.sup.2 -terbutyl-N.sup.4 -ethyl-6-methylthio-1,3,5-triazine-                                          520                                                  2,4-diyldiamine (Terbutryn)                                                   Silicon dioxide (silica) 50                                                   Aluminum-Silicate (clay) 363                                                  Sulphonated Napthalene Condensate (Dispersant)                                                         60                                                   Alkylated Napthalene Sulphonate (Dispersant)                                                           7                                                    TOTAL                    1000                                                 ______________________________________                                    

A mixture was prepared as reported as Example 3A and Example 3B in ratio1:1, using a shaker such as that used for similar paint products toproduce a final product with 50% (w/w) activity.

The biocide formulation was incorporated into a styrene-acrylic paintformulation and tested according to the method described in Example 1with similar synergistic results obtained.

                  TABLE 5                                                         ______________________________________                                        DISPERSION                                                                    Ingredient A                                                                              Part/Wt.                                                                              Ingredient B     Part/Wt.                                 ______________________________________                                        Propylene glycol                                                                          7       Propylene glycol 7                                        3-iodo-2-propynyl                                                                         42      N.sup.2 -terbutyl-N.sup.4 -ethyl-6-                                                            42                                       butyl carbamate     methylthio-1,3,5-triazine-2,4-                            (IPBC)              diytdiamine (Terbutryn)                                   Aerosil (Hydrophobic                                                                      1       Aerosil (Hydrophobic Silica)                                                                   1                                        Silica)                                                                       Mix                                                                           Dispersant  2.0                      2.0                                      (Nonylethoxylate)                                                             Wetting Agent                                                                             1.0     Wetting Agent    1.0                                      (Ethoxylated Sulphate)                                                                            (Ethoxylated Sulphate)                                    Wetting Agent                                                                             1.0     Wetting Agent    1.0                                      (Ethoxylated Sulphate)                                                                            (Ethoxylated Sulphate)                                    Water       34.40   Water            34.40                                    Thickener   1.0     Thickener        1.0                                                  1.00                     100                                      ______________________________________                                    

Ingredients A and B as shown in Table 5 were made using a dispersingmill (with cooling mantle) and using 1 mm glass beads to a finenessgrind 5 microns or less. Some of the water may be omitted in order toobtain a thicker grinding paste as desired.

A mixture of A and B was made by combining the ingredients in a ratio of1:1 to produce a synergistic combination product of the algaecide andthe fungicide.

This product was then mixed into a styrene-acrylic paint using alaboratory mixer for a 5 minute mixing period. It was tested asdescribed in Example 1 with similar results.

While certain specific embodiments of the invention have been describedwith particularity herein, it will be recognized that variousmodifications thereof will occur to those skilled in the art and it isto be understood that such modifications and variations are to beincluded within the preview of this application and the spirit and scopeof the appended claims.

We claim:
 1. A biocidal composition comprising a mixture of ahalopropynyl compound and a sulfur-containing s-triazine in a proportionthat exhibits synergistic biocidal activity, wherein said halopropynylcompound is 3-iodo-2-propynylbutyl carbamate and wherein saidsulfur-containing s-triazine is N² -tert-butyl-N⁴-ethyl-6-methylthio-1,3,5-triazine-2,4-diyldiamine and wherein thehalopropynyl compound and the sulfur-containing s-triazine are eachpresent in a synergistic effective amount of from about 1 parthalopropynyl compound to 9 parts s-triazine to about 9 partshalopropynyl compound to 1 part s-triazine.
 2. The composition of claim1 containing from about 0.004% to 2.0% of the mixture of saidhalopropynyl compound and said s-triazine.
 3. The biocidal compositionof claim 1 wherein said synergistic amount comprises from about 1 parthalopropynyl compound to 2 parts s-triazine to about 2 partshalopropynyl compound to 1 part s-triazine.
 4. A method of preparing thecomposition of claim 1 comprising mixing said halopropynyl compound andsaid sulfur-containing s-triazine in a liquid vehicle.
 5. A method forprotecting a substrate from fungal or algael infestation comprisingtreating said substrate with an effective amount of the composition ofclaim
 1. 6. A biocidal composition comprising a solution of ahalopropynyl compound and a sulfur-containing s-triazine in a suitablesolvent, wherein said halopropynyl compound is 3-iodo-2-propynylbutylcarbamate and wherein said sulfur-containing s-triazine is N²-tert-butyl-N⁴ -ethyl-6-methylthio-1,3,5-triazine-2,4-diyldiamine andwherein the halopropynyl compound and the sulfur-containing s-triazineare each present in a synergistic effective amount of from about 1 parthalopropynyl compound to 9 parts s-triazine to about 9 partshalopropynyl compound to 1 part s-triazine.
 7. The biocidal compositionof claim 6 wherein said synergistic amount comprises from about 1 parthalopropynyl compound to 2 parts s-triazine to about 2 partshalopropynyl compound to 1 part s-triazine.
 8. A method of preparing thecomposition of claim 6 comprising dissolving said halopropynyl compoundand said sulfur-containing s-triazine in a solvent.
 9. A method forprotecting a substrate from fungal or algael infestation comprisingtreating said substrate with an effective amount of the composition ofclaim 6.